Method for preparing crystalline zirconium phosphates

ABSTRACT

A new crystalline zirconium phosphate composition and method for its synthesis are provided. The composition has ion exchange properties and is readily convertible to catalytically active material by thermal treatment.

This is a continuation of copending application Ser. No. 676,968, filedon Nov. 30, 1984 now abandoned

The present invention relates to a method of preparing zirconiumphosphates in the presence of a bulky organic cation. The resultingmaterial exhibits thermal stability, ion exchange properties, sorptioncapacity and distinct X-ray diffraction patterns.

Crystalline zirconium phosophates are known to exhibit a capacity forion exchange. Alpha zirconium phosphate Zr(HPO₄)₂.H₂ O is known to havea small interlayer radius (7.6 angstroms) which results in slow exchangeof cations having a large ionic radius such as Cs⁺, Ba²⁺ and hydratedMg²⁺. A more highly hydrated form of zirconium phosphate, theta,variously reported as Zr(HPO₄)₂.8H₂ O and Zr(HPO₄)₂.6H₂ O, exhibitsimproved cation exchange properties probably owing to its greaterinterlayer spacing of 10.4 angstroms. Clearfield et al., J. Inorg. Nuc.Chem. 1964, Vol. 26, pp. 117 to 129, Pergamon Press. The anhydrous phaseof zirconium phosphate Zr(HPO₄)₂, known as beta zirconium phosphate, andthe dihydrate phase, gamma zirconium phosphate Zr(HPO₄)₂.2H₂ O alsoexhibit greater interlayer distance than the alpha form with d-spacingsof 9.4 and 12.2 angstroms, respectively. Clearfield et al., J. Inorg.Nuc. Chem. 1968, Vol. 30 pp. 2249-2258, Pergamon Press. Like the thetaform, these zirconium phosphates of increased interlayer spacing arecapable of ion-exchanging bulky cations at a greater rate than the alphaform.

The above zirconium phosphates are normally prepared by addition of asoluble salt of zirconium to a solution of phosphoric acid or a solublesulfate. In the presence of an excess of the phosphorus derivative,i.e., P:Zr mole ratio >2, a gel is formed with crystallizes when thereactant mixture is maintained at elevated temperature for an extendedtime, say about 48 hours. Other methods of producing zirconiumphosphates are set out in U.S. Pat. Nos. 3,056,647; 3,485,763; 4,025,608and 4,381,289, all of which are incorporated herein by reference.

Although the resulting materials exhibit a significant ion exchangecapability, they suffer from limitations in thermal stability. Attemperatures above about 300° C. such materials are subject to losses insorption and surface acidity.

Zirconium phosphonates have been prepared by reacting organics such asethylene oxide with the acidic hydroxyl of the layered zirconiumphosphate to convert the inorganic acid hydroxyls to bound organicalkanol groups. See, e.g. Yamaka, Inorg. Chem 15, 2811, (1976). Otherphosphonates of zirconium including zirconium bis(benzenephosphonate),zirconium bis(hydroxymethanephosphonate) monohydrate and zirconiumbis(monoethylphosphonate) have been prepared. Alberti et al., J. Inorg.Nucl. Chem., 40, 1113 (1978), U.S. Pat. No. 4,298,723 to DiGiacomo etal., incorporated herein by reference describes a process for preparinglayered materials similar in structure to zirconium phosphates. A sourceof zirconium such as zirconyl chloride is combined with anorganophosphorus acid compound of the formula ((HO)₂ OP)_(n) R, whereinn is 1 or 2 and R may be an acyclic group, heteroacyclic groupcontaining one or more heteroatoms selected from O, N, and S, a cyclicgroup, aromatic group, or a heterocyclic group containing one or moreheteroatoms selected from O, N and S. The organo groups occupy anaverage surface area not greater than about 24 square angstroms in eachsection bounded by four zirconium atoms. The resulting layered materialexhibit improved thermal stability over prior art zirconium phosphates.

It has now been found that crystalline zirconium phosphates of highthermal stability and sorption capacity can be prepared by including abulky organic cations having a molecular weight greater than about 100,500, 1000 or even 10,000 in a forming mixture which contains a source ofzirconium and a source of phosphorus. Crystalline zirconium phosphatecompounds of the present invention include those having the composition:

    xA:yM'.sub.2/m O:ZrO.sub.2 zP.sub.2 O.sub.5 :wH.sub.2 O

where A is an organic cation having a molecular weight of at least about100; M' is a cation of valence m; 0<x<4; 0<y<6; 0<z<3; and 0<w<20. Suchmaterials can be prepared by combining a phosphorus source selected fromthe group consisting of water-soluble phosphates and phosphoric acid,with a salt of the organic cation, and thereafter combining theresulting mixture with a source of zirconium under crystallizationconditions. Cations of onium compounds are particularly useful inpreparing zirconium phosphates of the present invention. Onium compoundswhich may be usesd include those having the following formula:

    R.sub.p M.sup.+ X.sup.-

wherein R is alkyl of from 1 to 20 carbon atoms, heteroalkyl of from 1to 20 carbon atoms, aryl heteroaryl, cycloalkyl of from 3 to 6 carbonatoms, cycloheteroalkyl, of from 3 to 6 carbon atoms, or combinationsthereof; p is 1 to 4, preferably 4; M is a quadricoordinate element(e.g., nitrogen, phosphorus, arsenic, antimony or bismuth) or aheteroatom (e.g., N, O, S, Se, P, As, etc.) in an alicyclic,heteroalicyclic or heteroaromatic structure; and X is an anion (e.g.,fluoride, chloride bromide, iodide, hydroxide, acetate, sulfate,carboxylate, etc.). When M is a heteroatom in an alicyclic,heteroalicyclic or heteroaromatic structure, the cation R_(p) M⁺ may be,as non-limiting examples, ##STR1## wherein R' is alkyl of from 1 to 20carbon atoms, heteroalkyl of from 1 to 20 carbon atoms, aryl,heteroaryl, cycloalkyl of from 3 to 6 carbon atoms of cycloheteralkyl offrom 3 to 6 carbon atoms.

In particular, tetraalkylammonium compounds have been found to be usefulonium compounds in the present invention, e.g., tetrapropylammoniumbromide and tetrapropylammonium hydroxide. Compounds containing multiplecationic centers including cationic polymers known as ionomers, by alsobe used such as those having the formula:

    [(R).sub.3 M.sup.+ (Z).sub.n M.sup.+ (R).sub.3 ].sub.y (X.sup.-).sub.2n

where y >1

wherein R, M and X are as above defined, Z is a bridging member selectedfrom the group consisting of alkyl of from 1 to 20 carbon atoms, alkenylof from 2 to 20 carbon atoms, aryl, heteroalkyl of from 1 to 20 carbonatoms, heteralkenyl of from 2 to 20 carbon atoms and heteroaryl, and nis a number of from 1 to about 50. Non-limiting examples of suchmultiple cationic center containing compounds include:

[(CH₃)₃ As+(CH₂)₆ N+(CH₃)₃ ](Cl⁻)₂,

[(C₃ H₇)₃ N+(CH₂)₁₀ N+(C₃ H₇)₃ ](Cl⁻)₂,

[(C₆ H₅)₃ N+(C₂ H₄)₁₆ P+(C₆ H₅)₃ ](OH⁻)₂,

[(C₁₈ H₃₇)₃ P⁺ (C₂ H₂)₃ P+(C₃)₃ ](Cl⁻)₂,

[(C₂ H₅)₃ N+(C₆ H₄)N+(C₂ H₅)₃ ](Br⁻)₂,

[(CH₃)₃ Sb+(CH₂)₁₀ Sb+(CH₃)₃ ](Cl⁻)₂,

[(C₆ H₅)₃ Sb+(CH₂)₄ N+(CH₃)₃ ](OH⁻)₂,

[(C₂ H₃)₃ N+(CH₂)₅₀ N+(C₂ H₃)₃ ](OH⁻)₂,

[(C₆ H₅)₃ P+(C₂ H₂)₆ As+(CH₃)₃ ](Cl⁻)₂,

[(CH₃)₃ N+(CH₂)₆ N+(CH₃)₃ ](Cl⁻)₂, and ##STR2##

The cation may also be a quaternary phosphorus cation of a salt. Thephosphorus-containing salt may be of the type disclosed in U.S. Pat.Nos. 4,209,449 and 4,336,385 to Mayhew et al. incorporated hereby byreference, and available from Mona Industries, Paterson, N.J. Broadlyspeaking, such salts are of the formula: ##STR3## wherein R is anamidoamine moiety of the formula ##STR4## R¹ is alkyl, alkenyl, alkoxy,or hydroalkyl of from 5 to 22 carbon atoms each, or aryl or alkary of upto 20 carbon atoms,

R² is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atomseach or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5carbon atoms, or polyoxyalkalene of up to 10 carbon atoms;

R³ and R⁴, which may be the same or different, are selected from alkyl,hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl moiety,and polyoxyalkylene of up to 10 carbon atoms; in addition, R³ and R⁴taken together with the nitrogen to which they are attached, mayrepresent an N-containing heterocycle;

n is an integer from 2 to 12; and

X is an anion.

In a particularly preferred embodiment, R₁ is C₅ to C₁₇ alkyl, R₂ is H,R₃ and R₄ are methyl and n═3. In another preferred embodiment R₁ is C₁₁to C₁₃ alkyl and X is Cl.

In another embodiment, R may be ##STR5## and R⁵ is C₅ to C₁₇ alkyl, say,for example, C₁₂ alkyl, and X is Cl.

In still another embodiment the phosphorus-containing salt may comprisea zwitterion, for example, materials such as ##STR6## may be included inthe forming mixture.

Upon exposure to crystallization conditions a crystalline zirconiumphosphate compound is produced, having the composition:

    xA:yM.sub.2/m O:ZrO.sub.2 :zP.sub.2 O.sub.5 :wH.sub.2 O

where A is an organic cation of the salt described above; M is a cationof valence m; 0<x<4; 0<y<6; 0<z<3; and 0<w<20, preferably 0.01<x<2;1<y<4; 0.5<z<2; and 0<w<10.

The crystalline material of the present invention exhibits an X-raydiffraction pattern showing the significant lines set out below in Table1.

                  TABLE 1                                                         ______________________________________                                        d-space           2-theta I/I.sub.o                                           ______________________________________                                        11.33 +    0.1        7.79    m                                               3.89 +     0.05       22.87   s                                               3.29 +     0.03       27.05   vs                                              3.14 +     0.03       28.45   w-m                                             2.66 +     0.02       33.71   w                                               2.63 +     0.02       34.10   w                                               ______________________________________                                    

with I/I_(o) from 0 to 24%=w (weak), from 25 to 49%=m (medium), from 50to 75%=s (strong), and from 75 to 100%-vs (very strong).

While not wishing to be bound by theory, it is believed that thesurfactant and directing properties of the organic cations, as well astheir ability to ion-exchange during synthesis, advantageously affectthe gelation of the reactant mixture, the rheology of the obtained gelphase, as well as gel crystallization. The bulkiness of the cationsserve to keep the layers far apart during the reaction.

The zirconium phosphate materials of the present invention are made byreacting a source of zirconium and a source of phosphorus in thepresence of a bulky organic cation characterized above. Suitable sourcesof zirconium include zirconium water soluble compounds such as zirconylchloride, ZrOCl.8H₂ O. Suitable phosphorus sources include water solublephosphates or hydrogen phosphates such as NaH₂ PO₄. H₂ O,organophosphorus compounds, phosphorus oxides, and phosphoric acid.Preferably, the bulky organic cationic compound is combined with thephosphorus source, e.g., NaH₂ PO₄.H₂ O and where necessary, solution iseffected by adding an acid solution such as 3N HCl. The resultingmixture can be then refluxed, during which time the source of zirconium,e.g., a 1M ZrOCl₂.8H₂ O solution, is gradually added. The P/Zr molarratio of the resulting forming mixture, exclusive of added organiccation, is greater than 2. Upon addition of zirconium a gel is formed.Crystallization of the gel results from its exposure to refluxingconditions or by autoclaving. Temperatures greater than about 70° C.,preferably about 90° C. to 150° C., may be used in effectingcrystallization. The pressure may be atmospheric, autogeneous, or anysuitable crystallization pressure ranging from about 1 to 30 atm.Depending on the particular conditions employed, crystallization timecan range from 1 to 500 hours.

In those situations where an alkali metal-containing phosphorus salt isused as the phosphorus source e.g., a sodium salt of phosphoric acid,some or all ion-exchange sites of the resulting crystalline zirconiumphosphate material will be exchanged with alkali metal. In order toconvert such material to the proton exchanged from, the as-synthesizedcrystalline zirconium phosphate is acid washed. Proton-exchange ispreferably achieved by contacting the material to be exchanged, with amixture of hydrochloric and/or phosphoric acid, followed by rinsing withdistilled water.

Upon crystallization and any subsequent treatment such asproton-exchange or ammonium exchange, the crystalline material is dried.The drying step may be in any suitable atmosphere, including vacuum orair at temperature ranging from about 50° to 200° C., say about 120° C.

The dried crystalline zirconium phosphate may then be exposed to thermaltreatment, i.e. calcined in an inert gas atmosphere, such as nitrogen orhelium, and/or in an oxygen-containing atmosphere, e.g., air. Suitablecalcining temperatures can range from about 200° to 600° C., say aboute.g., 250° C. or 500° C. Such treatment results in removal of at leastsome of the organic cation present in the structure of the zirconiumphosphate.

The calcined materials exhibit thermal stability at temperatures of 400°C. or even higher. In addition, these materials possess strong acidsites and enhanced surface acidity. Accordingly, the zirconium phosphatematerials of the present invention are significantly better than priorart zirconium phosphates which exhibit poor thermal stability andreduction in surface acidity when exposed to temperature above 300° C.Thus, the present invention may be used to prepare zirconium phosphateswhich may be used as ion exchangers or catalysts under a wide variety ofoperating conditions and temperatures. For example, they may be used intheir acid form for acid-catalyzed reactions. Ion-exchange of thezirconium phosphate with metal ions yields a catalyst suitable foroxidation or base-catalyzed reactions. The zirconium phosphates of thepresent invention may be employed in converting organic compounds bycontacting said compounds with the zirconium phosphates at conversionconditions. In addition, the products of the invention may be used as acatalyst binder owing to their thermal stability.

The following examples further describe the invention but are not to beconsidered limiting in any way.

EXAMPLES 1-10 Preparation of Zirconium Phosphates

A series of zirconium phosphate compounds, ZP-1 through ZP-10,corresponding to the product of Examples 1 through 10 were prepared inaccordance with Table 2. ZP-1 and ZP-9 were conventionally prepared inthe absence of bulky organic ions in the forming mixture. The remainingmaterials were prepared in the presence of organic ions derived fromquaternary ammonium compounds such as tetrapropylammonium bromide(TPABr), tetrapropylammonium hydroxide (TPAOH) and Monaquat PT-Z, acompound having the formula: ##STR7##

                                      TABLE 2                                     __________________________________________________________________________    SYNTHESIS AND CHARACTERISTICS OF ZIRCONIUM PHOSPHATES                         Designation   ZP-1                                                                             ZP-2                                                                              ZP-3                                                                             ZP-4                                                                              ZP-5                                                                              ZP-6                                                                              ZP-7                                                                              ZP-8                                                                              ZP-9                                                                              ZP-10                         __________________________________________________________________________    Reaction Mixture (g)                                                          Na--phosphate 68 68  68 68  68  68  68  68  68  68                            Zr--oxychloride                                                                             8  8   8  8   8   8   8   8   8   8                             HCl           5.5                                                                              5.5 5.5                                                                              5.5 5.5 5.5 5.5 5.5 5.5 5.5                           Water         75 75  75 75  130 75  100 75  75  75                            Organic Cmpd. -- A   A  A   B   A   A   A   --  C                             A = TPABr                                                                     B = TPAOH                                                                     C = Monaquat PT-Z                                                             Organic (g)   -- 132 40 40  19  40  40  40  --  10                            Temperature (°C.)                                                                    95 95  95 135 95  135 135 135 135 135                           Time (hrs)    25 25  25 25  25  48  25  168 25  25                            Product composition (wt. %)                                                   C             -- 0.1 0.1                                                                              2.3 4.0 0.3 3.6 4.4 --  14.9                          N             -- --  -- 0.1 0.2 --  --  0.2 --  0.2                           Na            6.0                                                                              3.8 4.3                                                                              6.1 9.9 5.3 0.5 14.2                                                                              8.3 2.8                           Cl            -- n.t.                                                                              n.t.                                                                             n.t.                                                                              2.5 0.1 --  2.3 1.6 1.3                           Zr            29.1                                                                             29.6                                                                              29.9                                                                             28.8                                                                              20.8                                                                              27.2                                                                              26.9                                                                              18.3                                                                              22.6                                                                              20.3                          P             20.5                                                                             20.9                                                                              20.3                                                                             19.7                                                                              20.6                                                                              19.7                                                                              19.9                                                                              19.8                                                                              21.9                                                                              17.2                          Product molar composition                                                     PZr           2.06                                                                             2.07                                                                              1.99                                                                             2.01                                                                              2.91                                                                              2.12                                                                              2.17                                                                              3.17                                                                              2.83                                                                              2.49                          Na/P          0.39                                                                             0.25                                                                              0.29                                                                             0.42                                                                              0.65                                                                              0.36                                                                              0.03                                                                              0.97                                                                              0.51                                                                              0.22                          Adsorption (n-hexane, wt.                                                     %, at 30° C.)                                                          Calc. 250 C   1.20                                                                             1.80                                                                              -- 1.72                                                                              0.73                                                                              2.10                                                                              --  0.95                                                                              0.12                                                                              1.80                          Calc. 500 C   1.20                                                                             1.60                                                                              0.90                                                                             1.77                                                                              0.33                                                                              2.30                                                                              --  1.12                                                                              0.00                                                                              2.10                          __________________________________________________________________________

The materials of the present invention were prepared as follows:

The organic cation compound and 68 g of NaH₂ PO₄ H₂ O were dissolved in50 ml of 3N HCl at reflux 25.0 ml of 1M ZrOCl₂.8H₂ O was then addeddropwise over a period of about 30 mins. A gel resulted which wascrystallized by autoclaving at 135° C. or refluxing at about 95° C. forabout 25 to 170 hours. The crystallized sodium-exchanged product wasthen filtered and washed. Sodium ion was proton-exchanged by acidwashing in 2N HCl and 0.2M H₃ PO₄ followed by rinsing with distilledwater. The acid forms of the zirconium phosphate was then dried in anoven at 120° C.

EXAMPLE 11 Thermal Stability of Zirconium Phosphate

X-ray diffraction patterns of ZP-4, a zirconium phosphate prepared froma forming mixture which contains tetrapropylammonium bromide wereobtained by standard techniques for as-synthesized ZP-4, ZP-4 calcinedat 350° C., and ZP-4 calcined at 500° C. The X-ray diffractograms weresubstantially the same except for minor shafts in interplanar spacingand variation in relative intensity. Thus, it is seen that ZP-4 isthermally stable even at temperatures of 500° C.

EXAMPLE 12 X-Ray Diffraction Pattern of Treated ZP-4

ZP-4 was treated by NaOH according to the following procedure:

(1) Add 1.0 g ZP-4 (as synthesized) to 130 mg NaOH in 200 ml water.

(2) Stir for 3 hours at ambient temperature.

(3) Filter, without washing, and dry at 100° C.

Another sample of ZP-4 was treated with dimethylsilane by heating 2.0 gZP-4 to 250° C. (5°/min), while flowing dimethylsilane continuouslythrough the reactor at 60 cc/min.

X-ray diffraction patterns of the samples were then obtained byconventional methods. A comparison of the two patterns showed that thecrystalline structure was essentially maintained, as minor shifts onlyoccurred in interplanar spacings. Furthermore, the uptake ofdimethylsilane, a material which is relatively inert to weakly acidicconditions, indicates the presence of very strong acid sites in thepartially protonated form of ZP-4.

EXAMPLE 13 Reproducibility of ZP-4 Synthesis

Another batch of ZP-4 was prepared according to the procedure of Example4. A comparison of X-ray diffraction patterns of the materials ofExamples 4 and 13, indicated the reproducibility of the synthesisproduct.

What is claimed is:
 1. A method for preparing in an aqueous reactionmixture crystalline zirconium phosphate compounds having thecomposition:

    xA:yM'.sub.2/m O:ZrO.sub.2 :zP.sub.2 O.sub.5 :wH.sub.2 O

where A is an organic cation having a molecular weight of at least about100; M' is a cation of valence m; 0<x<4; 0<y<6; 0<z<3; and 0<w<20,wherein a phosphorus source selected from the group consisting ofwater-soluble phosphates and phosphoric acid is combined with a salt ofsaid organic cation, and thereafter combined with a source of zirconiumunder crystallization conditions.
 2. The method of claim 1 wherein saidphosphorus source comprises NaH₂ PO₄.H₂ O; said source of zirconium isZrOCl₂.8H₂ O; 0.01<x<2; 1<y<4; 0.5<z<2; and 0<w<10.
 3. The method ofclaim 1 wherein said organic cation is a cation of the compound

    R.sub.4 M.sup.+ X.sup.-

wherein R is selected from the group consisting of alkyls of from 1 to20 carbon atoms, heteroalkyls of from 1 to 20 carbon atoms, aryls,heteroaryls, cycloalkyls of from 3 to 6 carbon atoms, cycloheteroalkyls,of from 3 to 6 carbon atoms; M is a quadricoordinate element selectedfrom the group consisting of nitrogen, phosphorus, arsenic, and antimonyand X is an anion selected from the group consisting of fluoride,chloride, bromide, iodide, hydroxide, acetate, sulfate, and carboxylate.4. The method of claim 3 wherein R is an alkyl of from 1 to 20 carbonatoms and M is nitrogen.
 5. The method of claim 4 wherein R is propyl.6. The method of claim 1 wherein said organic cation is a cation of thesalt

    R.sub.p M.sup.+ X.sup.-

wherein R is selected from the group consisting of alkyls of from 1 to20 carbon atoms, heteroalkyls of from 1 to 20 carbon atoms, aryls,heteroaryls, cycloalkyls of from 3 to 6 carbon atoms, cycloheteroalkyls,of from 3 to 6 carbon atoms; p is 1 to 4; M is a heteroatom selectedfrom the group consisting of nitrogen, oxygen, sulfur, selenium,phosphorus and arsenic in a structure selected from the group consistingof alicyclics, heteroalkicyclics, and heteroaromatics; and X is an anionselected from the group consisting of fluoride, chloride, bromide,iodide, hydroxide, acetate, sulfate, and carboxylate.
 7. The method ofclaim 6 wherein said organic cation is selected from the groupconsisting of ##STR8## wherein R' is selected from the group consistingof alkyl of from 1 to 20 carbon atoms, heteroalkyl of from 1 to 20carbon atoms, aryl, heteroaryl, cycloalkyl of from 3 to 6 carbon atomsand cycloheteroalkyl of from 3 to 6 carbon atoms.
 8. The method of claim1 wherein said salt is of the formula: ##STR9## wherein R is anamidoamine moiety of the formula ##STR10## wherein R¹ is selected fromthe group consisting of alkyl, alkenyl, alkoxy, and hydroxyalkyl of from5 to 22 carbon atoms each; and aryl or alkaryl of up to 20 carbonatoms,R² is selected from the group consisting of hydrogen, alkyl,hydroxyalkyl or alkenyl of up to 6 carbon atoms each; cycloalkyl of upto 6 carbon atoms and polyoxyalkylene of up to 10 carbon atoms; R³ andR⁴, which may be the same or different, are selected from the groupconsisting of alkyl, hydroxyalkyl, carboxyalkyl of up to 6 carbon atomsin each alkyl moiety; polyoxyalkylene of up to 10 carbon atoms; and R³and R⁴ taken together with the nitrogen to which they are attached as anN-heterocycle; n is an integer from 2 to 12; and X is an anion.
 9. Themethod of claim 8 wherein R₁ is C₅ to C₁₇ alkyl, R₂ is H, R₃ and R₄ aremethyl and N+3.
 10. The method of claim 9 wherein R₁ is C₁₁ to C₁₃ alkyland X is Cl.
 11. The method of claim 6 wherein R is ##STR11## and R⁵ isC₅ to C₁₇ alkyl.
 12. The method of claim 11 wherein R⁵ is C₁₂ alkyl andX is Cl.
 13. The method of claim 12 wherein 0.01<x<1; 1<y<4; 0.5<z<2;and 0<w<10.
 14. The method of claim 1 wherein said crystallizationcondition include crystallization under reflux.
 15. The method of claim1 wherein said crystallization conditions comprise temperatures greaterthan about 100° C.
 16. The method of claim 14 wherein the crystallizedproduct is proton-exchanged by acid washing.
 17. The method of claim 16wherein said acid washing is effected by contacting the crystallizedproduct with about 2N HCl and 0.2M H₃ PO₄.
 18. The method of claim 15wherein the crystallized product is proton-exchanged by acid washing.19. The method of claim 18 wherein said acid washing is effected bycontacting the crystallized product with 2N HCl and 2M H₃ PO₄.
 20. Themethod of claim 16 wherein the proton-exchanged product is dried atabout 50° to 200° C.
 21. The method of claim 18 wherein theproton-exchanged product is dried at about 50° to 200° C.
 22. Acrystalline zirconium phosphate compound having the composition:

    xA:yM'.sub.2/m O:ZrO.sub.2 :zP.sub.2 O.sub.5 :wH.sub.2 O

where A is an organic cation; M' is a cation of valence m; .[.Ox4; Oy6;Oz3; Ow20; .]. .Iadd.O<x<4; O<y<6; O<z<3; O<w<20; .Iaddend.and havingthe significant X-ray diffraction lines of Table 1 of the specification.23. The compound of claim 22 wherein said organic cation is a cation ofthe salt

    R.sub.4 M.sup.+ X.sup.-

wherein R is selected from the group consisting of alkyls of from 1 to20 carbon atoms, heteroalkyls of from 1 to 20 carbon atoms, aryls,heteroaryls, cycloalkyls of from 3 to 6 carbon atoms, cycloheteroalkyls,of from 3 to 6 carbon atoms; M is a quadricoordinate element selectedfrom the group consisting of nitrogen, phosphorus, arsenic, and antimonyand X is an anion selected from the group consisting of fluoride,chloride, bromide, iodide, hydroxide, acetate, sulfate, and carboxylate.24. The compound of claim 23 wherein R is an alkyl of from 1 to 20carbon atoms and M is nitrogen.
 25. The compound of claim 24 wherein Ris propyl.
 26. The compound of claim 22 wherein said organic cation is acation of the salt PS

    R.sub.4 M.sup.+ X.sup.-

wherein R is selected from the group consisting of alkyls of from 1 to20 carbon atoms, heteroalkyls of from 1 to 20 carbon atoms, aryls,heteroaryls, cycloalkyls of from 3 to 6 carbon atoms, andcycloheteroalkyls of from 3 to 6 atoms; M is a heteroatom selected fromthe group consisting of nitrogen, oxygen, sulfur, selenium, phoshorusand arsenic in a structure selected from the group consisting ofalicyclics, heteroalicyclics, and heteroaromatics; and X is an anionselected from the group consisting of fluoride, chloride, bromide,iodide, hydroxide, acetate, sulfate, and carboxylate.
 27. The compoundof claim 26 wherein M is selected from the group consisting of ##STR12##wherein R' is selected from the group consisting of alkyl of from 1 to20 carbon atoms, heteroalkyl of from 1 to 20 carbon atoms, aryl,heteroaryl, cycloalkyl of from 3 to 6 carbon atoms and cycloheteroalkylof from 3 to 6 carbon atoms.
 28. The compound of claim 22 wherein A isan organic phosphate quaternary cation.
 29. The compound of claim 22wherein A is ##STR13## wherein R is an amidoamine moiety of the formula##STR14## wherein R¹ is selected from the group consisting of alkyl,alkenyl, alkoxy, hydroxyalkyl, of from 5 to 22 carbon atoms each, andaryl or alkaryl of up to 20 carbon atoms,R² is selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, alkenyl, of up to 6 carbonatoms each; cycloalkyl of up to 6 carbon atoms; and polyoxyalkylene ofup to 10 carbon atoms; R³ and R⁴, which may be the same or different,are selected from the group consisting of alkyl, hydroxyalkyl,carboxyalkyl, of up to 6 carbon atoms in each alkyl moiety;polyoxyalkylene of up to 10 carbon atoms; and R³ and R⁴ taken togetherwith the nitrogen to which they are attached, as an N-heterocycle; and nis an integer from 2 to 12;
 30. The compound of claim 29 wherein R₁ isC₅ to C₁₇ alkyl, R₂ is H, R₃ and R₄ are methyl and n=3.
 31. The compoundof claim 30 wherein R₁ is C₁₁ to C₁₃ alkyl.
 32. The compound of claim 29wherein R is ##STR15## and R⁵ is C₅ to C₁₇ alkyl.
 33. The compound ofclaim 32 wherein R⁵ is C₁₂ alkyl.
 34. The compound of claim 33 wherein0.01<x<1; 1<y<4; 0.5<z<2; and 0<w<10.
 35. A crystalline zirconiumphosphate resulting from thermal treatment of the compound of claim 22.36. A crystalline zirconium phosphate resulting from thermal treatmentof the compound of claim
 23. 37. A crystalline zirconium phosphateresulting from thermal treatment of the compound of claim
 24. 38. Acrystalline zirconium phosphate resulting from thermal treatment of thecompound of claim
 25. 39. A crystalline zirconium phosphate resultingfrom thermal treatment of the compound of claim
 26. 40. A crystallinezirconium phosphate resulting from thermal treatment of the compound ofclaim
 29. 41. A crystalline zirconium phosphate resulting from thermaltreatment of the compound of claim
 32. 42. A crystalline zirconiumphosphate resulting from thermal treatment of the compound of claim 33.